CA2079888C - Process for preparing 2-acylglycerides or 1,2-diacyl diglycerides or 2,3diacyl diglycerides - Google Patents
Process for preparing 2-acylglycerides or 1,2-diacyl diglycerides or 2,3diacyl diglyceridesInfo
- Publication number
- CA2079888C CA2079888C CA002079888A CA2079888A CA2079888C CA 2079888 C CA2079888 C CA 2079888C CA 002079888 A CA002079888 A CA 002079888A CA 2079888 A CA2079888 A CA 2079888A CA 2079888 C CA2079888 C CA 2079888C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- group
- triglyceride
- diacyl
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 33
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004367 Lipase Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 230000000707 stereoselective effect Effects 0.000 claims abstract description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 15
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 14
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012062 aqueous buffer Substances 0.000 claims abstract description 7
- 108090001060 Lipase Proteins 0.000 claims description 29
- 102000004882 Lipase Human genes 0.000 claims description 29
- 229930195733 hydrocarbon Natural products 0.000 claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 235000019421 lipase Nutrition 0.000 claims description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 21
- 239000000194 fatty acid Substances 0.000 claims description 21
- 229930195729 fatty acid Natural products 0.000 claims description 21
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 108090000790 Enzymes Proteins 0.000 claims description 17
- 102000004190 Enzymes Human genes 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 17
- 235000019198 oils Nutrition 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- -1 alkyl hydrocarbons Chemical class 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 claims description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 235000019485 Safflower oil Nutrition 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- 235000005713 safflower oil Nutrition 0.000 claims description 3
- 239000003813 safflower oil Substances 0.000 claims description 3
- 235000020238 sunflower seed Nutrition 0.000 claims description 3
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 claims 2
- 235000006008 Brassica napus var napus Nutrition 0.000 claims 2
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 claims 2
- 244000188595 Brassica sinapistrum Species 0.000 claims 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 claims 2
- 235000005687 corn oil Nutrition 0.000 claims 2
- 239000002285 corn oil Substances 0.000 claims 2
- 150000003626 triacylglycerols Chemical class 0.000 abstract description 32
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 16
- 230000007062 hydrolysis Effects 0.000 abstract description 14
- 125000005456 glyceride group Chemical group 0.000 abstract description 10
- 238000005886 esterification reaction Methods 0.000 abstract description 9
- 230000032050 esterification Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000008707 rearrangement Effects 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000003925 fat Substances 0.000 description 17
- 235000019197 fats Nutrition 0.000 description 17
- 235000011187 glycerol Nutrition 0.000 description 15
- 150000004671 saturated fatty acids Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000004667 medium chain fatty acids Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 5
- 150000004668 long chain fatty acids Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000003441 saturated fatty acids Nutrition 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 108010048733 Lipozyme Proteins 0.000 description 3
- 230000010933 acylation Effects 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 3
- IJVLPVWXJLKHID-UHFFFAOYSA-N docosanoyl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCCCCCC IJVLPVWXJLKHID-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- LILCXMJACQHTHI-UHFFFAOYSA-N (1-decanoyloxy-3-hydroxypropan-2-yl) docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC(CO)COC(=O)CCCCCCCCC LILCXMJACQHTHI-UHFFFAOYSA-N 0.000 description 2
- ZYVCKYNTDUMOCT-UHFFFAOYSA-N (2-decanoyloxy-3-octanoyloxypropyl) docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCC)OC(=O)CCCCCCCCC ZYVCKYNTDUMOCT-UHFFFAOYSA-N 0.000 description 2
- CSPQFUGHYJVYJM-UHFFFAOYSA-N (3-hydroxy-2-octanoyloxypropyl) docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCC CSPQFUGHYJVYJM-UHFFFAOYSA-N 0.000 description 2
- NIZDYFWLWAFJLJ-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl octanoate Chemical compound CCCCCCCC(=O)OC(CO)CO NIZDYFWLWAFJLJ-UHFFFAOYSA-N 0.000 description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000235527 Rhizopus Species 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229940110456 cocoa butter Drugs 0.000 description 2
- 235000019868 cocoa butter Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- HTWWKYKIBSHDPC-UHFFFAOYSA-N decanoyl decanoate Chemical compound CCCCCCCCCC(=O)OC(=O)CCCCCCCCC HTWWKYKIBSHDPC-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000002316 solid fats Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 2
- JNSADKYBIPGQNK-UHFFFAOYSA-N (1-decanoyloxy-3-octanoyloxypropan-2-yl) docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC(COC(=O)CCCCCCC)COC(=O)CCCCCCCCC JNSADKYBIPGQNK-UHFFFAOYSA-N 0.000 description 1
- XLPIKANZEWEIDY-UHFFFAOYSA-N (2-decanoyloxy-3-hydroxypropyl) docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCC XLPIKANZEWEIDY-UHFFFAOYSA-N 0.000 description 1
- QVDPSOBUOWTYAN-UHFFFAOYSA-N 1,3-di(decanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC(COC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC QVDPSOBUOWTYAN-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- IYVVKFYDGRJWTR-UHFFFAOYSA-N 2-decanoylglycerol Chemical compound CCCCCCCCCC(=O)OC(CO)CO IYVVKFYDGRJWTR-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 240000006439 Aspergillus oryzae Species 0.000 description 1
- 235000002247 Aspergillus oryzae Nutrition 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 241000273930 Brevoortia tyrannus Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000283153 Cetacea Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000252203 Clupea harengus Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000019487 Hazelnut oil Nutrition 0.000 description 1
- 101001091385 Homo sapiens Kallikrein-6 Proteins 0.000 description 1
- 102100034866 Kallikrein-6 Human genes 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- DNULQWTYMFQUHB-UHFFFAOYSA-N MG(0:0/22:0/0:0) Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC(CO)CO DNULQWTYMFQUHB-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000498617 Mucor javanicus Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 241000235403 Rhizomucor miehei Species 0.000 description 1
- 240000005384 Rhizopus oryzae Species 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GGNALUCSASGNCK-UHFFFAOYSA-N carbon dioxide;propan-2-ol Chemical compound O=C=O.CC(C)O GGNALUCSASGNCK-UHFFFAOYSA-N 0.000 description 1
- 235000019879 cocoa butter substitute Nutrition 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 235000011850 desserts Nutrition 0.000 description 1
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013861 fat-free Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000010468 hazelnut oil Substances 0.000 description 1
- 235000019514 herring Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid group Chemical group C(CCCCC)(=O)O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009884 interesterification Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RAFYDKXYXRZODZ-UHFFFAOYSA-N octanoyl octanoate Chemical compound CCCCCCCC(=O)OC(=O)CCCCCCC RAFYDKXYXRZODZ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011945 regioselective hydrolysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000014438 salad dressings Nutrition 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010512 small scale reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6409—Fatty acids
- C12P7/6418—Fatty acids by hydrolysis of fatty acid esters
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
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Abstract
A process for the selective hydrolysis of triglycerides to 2-acyl glycerides is disclosed. This process uses a primary lower alkyl alcohol selected from the group consisting of methanol, the primary butanols and the primary pentanols and 2-butanol, an aqueous buffer system and a 1,3-lipase. The 2-acyl monoglycerides can be used to make stereospecific 1,2-diacyl glycerides or 2,3-diacyl glycerides through esterification with acid anhydrides and 1,3-lipase catalysis. Stereospecific 1,2,3-triglycerides can be made from these materials by standard esterification reactions under conditions which control rearrangement.
Description
~a~~s~~
Process For Preparing 2-Acylglycerides or 1,2-Diacyl Diglycerides or 2,3-Diacyl Diglycerides FIELD OF THE INVENTION
This invention relates to a lipase-catalyzed regio-and stereoselective preparation of triglycerides. These triglycerides are prepared by a synthetic route which involves regioselective hydrolysis of triglycerides to 2-acyl monoglycerides followed by regio- and stereoselective acylation of 2-acylglycerides to obtain specific triglyceride compounds.
BACKGROUND OF THE INVENTION
Monoglycerides are important food ingredients and surfactants. They are widely used in foods for emulsifiers and are found in salad dressings, creams, frozen desserts, shortenings and baked goods.
Monoglycerides are used for forming stable emulsions of oil and water as well as for complexing with starch and proteins. In addition, monoglycerides are useful for the synthesis of di- and triglycerides which are used in foods, drugs, and other consumer products.
Monoglycerides can also be used to derivatize other materials.
It has long been known that enzymic conversion of triglycerides to glycerol and fatty acids with 1,3-specific lipases, produces 2-monoglycerides as intermediates. However, only recently has this reaction been examined for practical preparation of 2-monoglycerides. In general these reactions have been carried out by transesterification or hydrolysis in mechanically formed microemulsions using enzyme catalysis. Both methods require nearly anhydrous conditions.
The stereoselective acylation of 2-monoglycerides to form regiospecific triglycerides is also important.
Cocoa butter ,.._.__.
WO 91/16442 PCT/US91/0?~
_ 2 _ substitutes, low calorie fats and other tailored triglycerides require such a synthesis.
BACKGROUND ART
European Patent Application 126,416 (Asahi Denka Koav~. 1984) describes a continuous transesterification of fat or oil using lipase enzymes. The lipase has 1,3-specificity and is fix~~ on a porous solid or Chitosan derivative as a carrier. Prefera~'y alcohols are added during the reaction. The most preferre~
alcohols are aliphatic alcohols having 4-18 carbons. The preferred are butyl, hexyl, octyl and decyl alcohols. The ~cvel of alcohol is 50-90 rol% of the free fatty acid estimates :c be produced. The level of water is controlled so that 1,2-diglycerides are formed. Fatty acid is then added to rake triglycerides. The water activity of the reaction mixture is from 0.5 to 0.9.
U.S. 4,865,978, issued to Serota (assigned U.S. Agric~~ltural Department, 1989) describes the hydrolysis of triglyceriec: to fatty acid and glycerol with lipase through the formation ;.f a "pseudo emulsion". The oil phase is divided into emulsic~ size particles suspended in~~the aqueous phase during mixing. ,~~se particles rapidly coalesce upon termination of the mixinc. The reaction is carried out at temperatures of ZOoC to 45oC.
European Patent Application 64,855, issued to Nailing et al.
(assigned Unilever, 1982) discloses transesterification cf fats by reaction in a water-immiscible organic liquid in contact w=~h an enzyme in a water phase (containing no more than 4% water;.
Glycerides are trans~sterified with a lipase enzyme in tfi~
presence of fat, oil or fatty acid. The lipase is immobi'ized on a solid.
Japanese 62,061.591 (assigned Kao, 1985) describes a interesterification reaction using an enzyme in the prese.-~~ of water, dihydric or trihydric alcohol (glycol or glycerol;. The' enzyme used is obtained by adding a water-insoluble carri~~ to a lipase containing medium which is then dried.
"'O 91 / 16442 PCT/US91 /02169 Japanese 61,173,791 (assigned Kao, 1986) describes the method for non-specific hydrolyzing oils using lipase in which the aqueous phase contained from 109'o to 40% glycerine. After hydrolysis an oily layer, an emulsion and an aqueous layer are formed. The emulsion layer is recovered and reused.
Japanese 62,278,988 (assigned Kao, 1987) discloses an enzymic or microbial reaction. Two phases are prepared, a non-aqueous solution and an aqueous solution. The reaction occurs at the interface of these two phases.
European patent application 237,092, filed by Holmberg (assigned Berol Kemi, 1987) describes a transesterification of triglycerides which is carried out in the presence of a lipase with a hydrophobic part (organic solvent) and a surface active component in water under strictly controlled conditions. Hexane 5 is used for the hydrophobic material. Both surfactants and auxiliary surfactants are used. Alcohols and glycol ethers are listed as surface active components, including butanol, pentanol and hexanol.
In general, the described processes require low water activity or other strictly controlled conditions. No practical methods were available to control the ratio of 2-acylglyceride to 1,2-diglycerides over a broad range. Although methods involving microemulsions reportedly gave good yields of 2-acyl glycerides, it was necessary to separate the monoglyceride from the 'S surfactant. This may not be easy due to the tendency of 2-acyl glycerides to rearrange to 1-acylglycerides when heated.
Accordingly, an economical process that would produce relatively pure 2-monoglycerides in high yield is desirable. The ability to produce high yields of 2-acyl-glycerides with little or '3 no 1,2-diacyl-glycerides or free glycerol is also highly desirable. It has been found that if the reaction is carried out in the presence of a lower alkyl alcohol selected from the group consisting of methanol, primary butanols and pentanols, and 2-butanol, the reaction proceeds in high yield to 'S 2-acylglycerides. The triglyceride is suspended in a water WO 91/16442 PCT/US91/02' -'' immiscible solvent, for example, hexane, and the lipase is dissolved in an aqueous buffer. The alcohol is added to the reaction mixture. It is surprising that this reaction occurs without the presence of added emulsifiers or surfactants, and the lipase can be recovered and reused.
A clear advantage of this new process is ability to control the course of hydrolysis by influencing the form of microstructures present in the reaction mixture. The hydrolysis generates products such as diglycerides, monoglycerides and acids known to undergo spontaneous formation of association structures, aggregates, microemulsions or liquid crystals if conditions permit. In particular, the presence cf an alcohol modifies these ~icrostructures, for example, it causes transition of liquid crystals to microemulsions. These Fh=nomena can have a profound effect on a course of the hydrolysis reaction. Thus, the control of hydrolysis can be achieved by pror~r selection of solvents, the alkyl alcohois described herein, without addition of emulsifiers.
It is accordingly an object of this invention to produce 2-acylmonoglycerides in yields of 80°.~ or more.
2~ Another aspect of this invention is the acylation of the monoglyceride in the presence of an eT~zyme with an acid anhydride to 1,2-diglycerides. 2-Acylglycerid~s can be isolated from the reaction mixture and used in the organic solvent in an acylation reaction using acid anhydrides.
Accordingly, it is the object of this invention to prepare regioselective 1,2-diglycerides or 2.3 diglycerides. These diglycerides can then be esterified to produce triglycerides through the use of a normal esterification reaction using acid chlorides or acid anhydrides. This esterification can be carried JO out using enzymic or chemical Catalysts.
All percentages herein are by weight unless otherwise indicated.
These and other objects of this invention will become obvious from the descriptions herein.
~~7 ~~~38 SUMMARY OF THE INVENTION
Described herein is a process for preparing 2 monoglycerides by enzymic hydrolysis comprising the steps of:
(1) preparing an aqueous solution of a lipase enzyme having a pH of 4 to about 8;
(2) forming a mixture of a water immiscible hydrocarbon, a lower alkyl alcohol selected from the group of methanol, primary butanols, primary pentanols and 2-butanol, and a triglyceride;
Process For Preparing 2-Acylglycerides or 1,2-Diacyl Diglycerides or 2,3-Diacyl Diglycerides FIELD OF THE INVENTION
This invention relates to a lipase-catalyzed regio-and stereoselective preparation of triglycerides. These triglycerides are prepared by a synthetic route which involves regioselective hydrolysis of triglycerides to 2-acyl monoglycerides followed by regio- and stereoselective acylation of 2-acylglycerides to obtain specific triglyceride compounds.
BACKGROUND OF THE INVENTION
Monoglycerides are important food ingredients and surfactants. They are widely used in foods for emulsifiers and are found in salad dressings, creams, frozen desserts, shortenings and baked goods.
Monoglycerides are used for forming stable emulsions of oil and water as well as for complexing with starch and proteins. In addition, monoglycerides are useful for the synthesis of di- and triglycerides which are used in foods, drugs, and other consumer products.
Monoglycerides can also be used to derivatize other materials.
It has long been known that enzymic conversion of triglycerides to glycerol and fatty acids with 1,3-specific lipases, produces 2-monoglycerides as intermediates. However, only recently has this reaction been examined for practical preparation of 2-monoglycerides. In general these reactions have been carried out by transesterification or hydrolysis in mechanically formed microemulsions using enzyme catalysis. Both methods require nearly anhydrous conditions.
The stereoselective acylation of 2-monoglycerides to form regiospecific triglycerides is also important.
Cocoa butter ,.._.__.
WO 91/16442 PCT/US91/0?~
_ 2 _ substitutes, low calorie fats and other tailored triglycerides require such a synthesis.
BACKGROUND ART
European Patent Application 126,416 (Asahi Denka Koav~. 1984) describes a continuous transesterification of fat or oil using lipase enzymes. The lipase has 1,3-specificity and is fix~~ on a porous solid or Chitosan derivative as a carrier. Prefera~'y alcohols are added during the reaction. The most preferre~
alcohols are aliphatic alcohols having 4-18 carbons. The preferred are butyl, hexyl, octyl and decyl alcohols. The ~cvel of alcohol is 50-90 rol% of the free fatty acid estimates :c be produced. The level of water is controlled so that 1,2-diglycerides are formed. Fatty acid is then added to rake triglycerides. The water activity of the reaction mixture is from 0.5 to 0.9.
U.S. 4,865,978, issued to Serota (assigned U.S. Agric~~ltural Department, 1989) describes the hydrolysis of triglyceriec: to fatty acid and glycerol with lipase through the formation ;.f a "pseudo emulsion". The oil phase is divided into emulsic~ size particles suspended in~~the aqueous phase during mixing. ,~~se particles rapidly coalesce upon termination of the mixinc. The reaction is carried out at temperatures of ZOoC to 45oC.
European Patent Application 64,855, issued to Nailing et al.
(assigned Unilever, 1982) discloses transesterification cf fats by reaction in a water-immiscible organic liquid in contact w=~h an enzyme in a water phase (containing no more than 4% water;.
Glycerides are trans~sterified with a lipase enzyme in tfi~
presence of fat, oil or fatty acid. The lipase is immobi'ized on a solid.
Japanese 62,061.591 (assigned Kao, 1985) describes a interesterification reaction using an enzyme in the prese.-~~ of water, dihydric or trihydric alcohol (glycol or glycerol;. The' enzyme used is obtained by adding a water-insoluble carri~~ to a lipase containing medium which is then dried.
"'O 91 / 16442 PCT/US91 /02169 Japanese 61,173,791 (assigned Kao, 1986) describes the method for non-specific hydrolyzing oils using lipase in which the aqueous phase contained from 109'o to 40% glycerine. After hydrolysis an oily layer, an emulsion and an aqueous layer are formed. The emulsion layer is recovered and reused.
Japanese 62,278,988 (assigned Kao, 1987) discloses an enzymic or microbial reaction. Two phases are prepared, a non-aqueous solution and an aqueous solution. The reaction occurs at the interface of these two phases.
European patent application 237,092, filed by Holmberg (assigned Berol Kemi, 1987) describes a transesterification of triglycerides which is carried out in the presence of a lipase with a hydrophobic part (organic solvent) and a surface active component in water under strictly controlled conditions. Hexane 5 is used for the hydrophobic material. Both surfactants and auxiliary surfactants are used. Alcohols and glycol ethers are listed as surface active components, including butanol, pentanol and hexanol.
In general, the described processes require low water activity or other strictly controlled conditions. No practical methods were available to control the ratio of 2-acylglyceride to 1,2-diglycerides over a broad range. Although methods involving microemulsions reportedly gave good yields of 2-acyl glycerides, it was necessary to separate the monoglyceride from the 'S surfactant. This may not be easy due to the tendency of 2-acyl glycerides to rearrange to 1-acylglycerides when heated.
Accordingly, an economical process that would produce relatively pure 2-monoglycerides in high yield is desirable. The ability to produce high yields of 2-acyl-glycerides with little or '3 no 1,2-diacyl-glycerides or free glycerol is also highly desirable. It has been found that if the reaction is carried out in the presence of a lower alkyl alcohol selected from the group consisting of methanol, primary butanols and pentanols, and 2-butanol, the reaction proceeds in high yield to 'S 2-acylglycerides. The triglyceride is suspended in a water WO 91/16442 PCT/US91/02' -'' immiscible solvent, for example, hexane, and the lipase is dissolved in an aqueous buffer. The alcohol is added to the reaction mixture. It is surprising that this reaction occurs without the presence of added emulsifiers or surfactants, and the lipase can be recovered and reused.
A clear advantage of this new process is ability to control the course of hydrolysis by influencing the form of microstructures present in the reaction mixture. The hydrolysis generates products such as diglycerides, monoglycerides and acids known to undergo spontaneous formation of association structures, aggregates, microemulsions or liquid crystals if conditions permit. In particular, the presence cf an alcohol modifies these ~icrostructures, for example, it causes transition of liquid crystals to microemulsions. These Fh=nomena can have a profound effect on a course of the hydrolysis reaction. Thus, the control of hydrolysis can be achieved by pror~r selection of solvents, the alkyl alcohois described herein, without addition of emulsifiers.
It is accordingly an object of this invention to produce 2-acylmonoglycerides in yields of 80°.~ or more.
2~ Another aspect of this invention is the acylation of the monoglyceride in the presence of an eT~zyme with an acid anhydride to 1,2-diglycerides. 2-Acylglycerid~s can be isolated from the reaction mixture and used in the organic solvent in an acylation reaction using acid anhydrides.
Accordingly, it is the object of this invention to prepare regioselective 1,2-diglycerides or 2.3 diglycerides. These diglycerides can then be esterified to produce triglycerides through the use of a normal esterification reaction using acid chlorides or acid anhydrides. This esterification can be carried JO out using enzymic or chemical Catalysts.
All percentages herein are by weight unless otherwise indicated.
These and other objects of this invention will become obvious from the descriptions herein.
~~7 ~~~38 SUMMARY OF THE INVENTION
Described herein is a process for preparing 2 monoglycerides by enzymic hydrolysis comprising the steps of:
(1) preparing an aqueous solution of a lipase enzyme having a pH of 4 to about 8;
(2) forming a mixture of a water immiscible hydrocarbon, a lower alkyl alcohol selected from the group of methanol, primary butanols, primary pentanols and 2-butanol, and a triglyceride;
(3) mixing the solutions from about 20°C to about 50°C for at least one hour; and (4) separating the phases and optionally recovering the 2-acylglyceride from the organic phase.
Also disclosed is a process for acylating a 2-acylglyceride by reacting an acid anhydride, immobilized lipase in a water immiscible solvent for from about 0.5 hours to about 5 hours at from about 20°C to about 50°C
temperature to form a stereoselective 1,2 diacylglyceride or 2,3-diglyceride.
Stereospecific 1,2,3-triacyl glycerols can be prepared by reacting the 1,2-diglycerides or 2,3-diglyceride with an acid anhydride or an acid chloride under anhydrous conditions in the presence of a chemical catalyst, e.g., 4-N,N-dimethylaminopyridine or an enzymic catalyst.
Other aspects of this invention are as follows:
A process for preparing 2-acylglycerides comprising:
(A) mixing the following ingredients for at least one hour at a temperature of from 20o C. to 50o C.
(1) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(2) from 20% to 60% of a water immiscible hydrocarbon;
(3) from 3% to 40% of a triglyceride:
~~i'~~~~
- 5a -(4) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglycerides;
(B) separating the water immiscible hydrocarbon containing -the 2-acylglyceride.
A process for preparing regiospecific 1,2-diacyl diglycerides or 2,3-diacyl diglycerides comprising the steps of:
(1) preparing a 2-monoacylglycerides by a process comprising:
(A) mixing the following ingredients for at least one hour at a temperature of from 20° C. to 50° C.:
(i) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(ii) from 20% to 60% of a water immiscible hydrocarbon (iii) from 3% to 40% of a triglyceride;
(iv) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglyceride;
(B) separating the immiscible hydrocarbon containing the 2-acylglyceride;
(2) reacting said 2-acylmonoglyceride with an acid anhydride, a catalytic amount immobilized lipase in a water immiscible hydrocarbon for from 0.5 hours to 5 hours at a temperature of from 20° C. to 50° C. to form a stereoselective 1,2-diacyl diglyceride or 2,3-diacyl diglyceride.
~.0~~8~8 - 5b -DETAILED DESCRIPTION OF THE INVENTION
Triglycerides prepared according to this invention generally have the formula:
C H O R' C HZ O R"
wherein R stands for an alkyl saturated or unsaturated fatty acid acyl group. R, R' and R" can be equal to each other.
The alkyl fatty acids used herein preferably have from about 2 to about 24 carbon atoms. Most preferably, the fatty acid in '~'O 91/16442 PCT/US91/02' '~
the 2 position has from 8 to 24 carbon atoms and fatty acids in the 1 and 3 positions, i.e. R and R", have from 8 to 24 carbon atoms. The fatty acids can be either saturated or unsaturated.
The unsaturated fatty acids can be mono unsaturated fatty acids or polyunsaturated fatty acids. The position occupied by R and R"
are the 1 and 3 positions, the position occupied by R' is the 2 position.
A. Definitions By "2-acylmonoglyceride" or "2-acylglyceride" is ~:eant a glycerol molecule esterified on the second carbon atoT: with a medium or long chain fatty acid.
By "medium chain fatty acid," as used herein, is :-.ant a saturated fatty acid, unsaturated fatty acid, or mixture thereof, having 6 to 10 carbon atoms.
By "medium chain fatty acid anhydride" as used herein, is meant the dehydration product of two medium chain fatty acids.
By "medium chain saturated fatty acid," as used herein, is meant C6 (caproic); Cg (caprylic), or C10 (capric) saturated fatty acids, or mixtures thereof. The C7 and Cg saturated fatty acids are not commonly found, but they are not excluded frog the possible medium chain fatty acids. The present media;- chain fatty acids do not include lauric acid (C12), sometimes referred to in the art as a medium chain fatty acid.
By "long chain fatty acid," as used herein, is meant a satu-rated fatty acid, unsaturated fatty acid, or mixture t!~~reof, havino 14 to 24 carbon atoms.
By "long chain saturated fatty acid," as used her~~n, is meant Clg (stearic), C1g {nonadecylic), C20 (arachidic'" C21 (heneicosanoic), C22 (behenic), C23 (tricosanoic), or C24 (lignoceric) saturated fatty acids, or mixtures there;.
As used herein, the term "comprising" means various components or steps can be conjointly employed in the :resent invention. Accordingly, the term "comprising" encompa:~es the more restrictive terms "consisting essentially of" and 'consisting of."
-"'~ 91 / 16442 ~ ~ ~ ~1 ~ ~ ~ PCT/US91 /02169 -All percentages, ratios and proportions used herein are by weight unless otherwise specified.
Hydrolysis of triglycerides to 2-monoacylglyceride is carried out in a two phase mixture of hydrocarbon and the starting triglycerides in a water immiscible phase and an aqueous phase comprising the buffer and a 1,3-specific lipase. The lower alkyl alcohol partitions between the aqueous phase and the organic phase.
The presence of alcohol has two functions. It inhibits hydrolysis of 2-acylglycerides to glycerol and it drives the reaction towards 2-monoglyceride. In its absence, the process reaches early steady state characterized by high concentrations of triglycerides and diglycerides. Thus, extension of the reaction time in the absence of alcohols would not result in better yielas of di- or monoglycerides but in the formation of glycerol. The higher straight chain alkyl alcohols, those having six or more carbon atoms, are less efficient or do not work. The alcohols that can be used herein are methanol, the primary butyl alcohols and the primary pentyl alcohols and 2-butanol. The preferred alcohols are 1-butanol, isobutanol and secondary butanol. The propyl alcohols do not work in this reaction nor does ethanol.
The primary butanols are 1-butanol and 2-methyl-1-propanol.
The primary pentanols are 1-pentanol, 2-methyl-1-butanol, and 3-methyl-1-butanol. The only secondary alcohol that functions :o produce the high yields of 2-acyl glycerides in the process of this invention is 2-butanol.
Any 1,3-specific lipase can be used for the hydrolysis. Tha ''0 lipases derived from the species asper9illus and rhizopus can be used. Specific lipases include aspergillus oryzae, aspergillus niger, mucor javanicus, mucor miehei, pancreatic, rhizopus delamar, rhizopus japonicus. These include MAP from Amano {Japan), lipolase and lipozyme from Novo (Netherlands). The amount of enzyme used is the amount of enzyme necessary to WO 91/16442 PCT/US91/0?.~~ '~
_ g _ catalyze the reaction at a reasonable rate. Too slow a rate will cause the concentration of diglycerides to increase.
The enzyme concentration depends upon the amount of active protein in the enzyme preparation. Enzyme can be dried, immobilized on a resin or covalently bonded to or abbsorbed on a support, or be in solution. The concentration needed to hydrolyze the triglyceride depends upon the form, the type and the activity of the enzyme. The amount required~is a catalytic amount. A
catalytic amount is enough to have the enzyme produce required 2-acyl glyceride at a reasonable rate but not so much as to force the reaction to form glycerine. One skilled in the art can easily determine the catalytic amount by running a small scale reaction and looking at the final products.
The triglyceride which has tt~,e requisite alkyl fatty acid in the 2 position is dissolved in a hydrocarbon. The preferred hydrocarbons are the hexanes, petroleum ether, or isooctane. Any water immiscible hydrocarbon solvent which is essentially inert to the lipase can be used. Some solvents can denature enzymes. The solvent must dissolve the triglyceride at the temperature of the reaction. Since these triglycerides can be used in foods and pharmaceuticals, a food approved or edible hydrocarbon should be used. The hydrocarbon can be an alkane with from 5 to 10 carbons, an aromatic hydrocarbon such as benzene, toluene or xylene or halogenated hydrocarbons such as chloroform, methylene chloride or carbon tetrachloride. The preferred hydrocarbon solvents are hexane, pentane, petroleum ether and isooctane.
From about 3% to about 60% triglyceride is used in the reaction. Triglycerides which can be utilized in the hydrolysis reaction include triglycerides ha~~ing C4 to C26 hydrocarbon chains with three fatty acid moieties. Ti'tese materials can be derived from plants or animals or can be edible synthetic fats or oils.
Liquid oils, e.g., unsaturated vegetable oils, can be used. Solid fats work only to the extent they are soluble in the solvent.
These oils can be partially hydrogenated to convert some of the unsaturated double bonds of the fatty acid constituents into "'~ 91/16442 ~ ~ ~ ~ ~~ ~ PCT/US91/02169 _g_ saturated bonds. Vegetable oils include soybean oil, hazelnut oil, linseed oil, olive oil, peanut oil, canola oil, safflower oil, rapeseed oil, cottonseed oil and sunflower seed oil can also be used herein.
Also suitable for use herein are the so-called low molecular weight synthetic fats which are certain tri- or diglycerides in which one or two of the hydroxyl groups of the glycerine have been esterified with acetic, propionic, butyric, hexanoic, capric or caprylic acids and one or two of the remaining hydroxyl groups of the glycerine have been esterified with a mixture of higher molecular weight fatty acids having from 8 to 22 carbon atoms.
Especially preferred for use herein are syr,Jretrical trigiycerides as, e.g., tridecanoin or trioctanoin.
Other common types of triglycerides include: cocoa butter and cocoa butter substitutes, such as shea and illipe butter; milk fats, such as butter fat; and marine oils which can be converted into plastic or solid fats such as menhaden, pilcherd, sardine, whale and herring oils.
Preferred triglycerides are those derived from vegetable oils. These can be hydrogenated and unhydrogenated oils.
Triglycerides of octanoic acid, decanoic acid and dodecanoic acid are preferred for use herein. Any unsaturated triglyceride containing unsaturated fatty acids is also preferred, e.g.
triolein. The triglycerides of long chain fatty acids are usually not soluble in the hydrocarbon solvent or are solid at the reaction temperature. Therefore they are not preferred for use herein.
The aqueous solution of the enzyme is buffered to a pH of about 4 to about 8. Standard buffer solutions which are not ~'0 incompatible with the enzyme can be used. These include the phosphate buffers.
The reaction mixture has the following proportions by weight percent:
3% to 40% triglyceride 15% to 25% aqueous buffer WO 91/16442 PCT/US91/02' ~~
2()'~9~~~ - to -lOX to 25% alcohol 20X to 60% hydrocarbon The preferred ratio of alcohol to triglyceride is based on the amount of fatty acid generated by the hydrolysis. The alcohol serves several functions in this reaction. It reacts with the fatty acid to make an alkyl ester driving the reaction toward the 2-acyl glyceride; and it modifies any association structures present in the reaction mixture. When the alcohol is insoluble in water, it can be substituted for the hydrocarbon if the triglyceride is soluble in the alcohol.
The reaction is carried out at ambient tempera~ure or at temperatures of from about 20oC to about 50oC for fr~~~~ 0.5 hours to about 8 hours. The reaction is mixed using a standard laboratory mixer.
The hydrocarbon layer is separated from the aquaous phase.
The 2-acylglyceride is present in the hydrocarbon phase. Any conventional separation technique can be used.
For example, the 2-acylglyceride can be isolated from the organic phase by crystallization or evaporation of the organic solvent. Liquid 2-acylmonoglycerides can be purified by distillation however, distillation frequently causes rearrangement or isomerization to 1-acyl-glycerides.
The 2-acylmonoglycerides can be esterified stereoselectively using acid anhydrides. It is not necessary to isolate the 2-monoacylglycerides from the organic phase if they are to be esterified. F!owever, the solution should be dried to less than about 0.5% water to prevent hydrolysis of the acid ~rhydride. Any suitable drying agent such as magnesium sulfate, calcium chloride or other inert drying aid can be used. Excess anhy3ride could also be used, but this is less economical.
The excess lower alkyl alcohol should also be removed since it too can react with the acid anhydride to form the corresponding ester.
The 2-monoacylglyceride is reacted with an acid anhydride in an organic solvent. Any hydrocarbon, either alkyl or aromatic, or halogenated hydrocarbon can be used for this reaction. For '- ~ 91/16442 ~ ~ ~ ~ ~ ~ PCT/US91/02169 example, petroleum ether, hexane, benzene, toluene, chloroform, methylene chloride and octane can be used.
A 1,3-specific lipase is added to the hydrocarbon mixture.
The same lipases as were used to prepare the 2-acylmonoglycerides are suitable for this reaction. They include immobilized lipases and liposomes which are preferred. Catalytic amounts of lipase are used.
Any acid anhydride can be used to esterify the 2-acylmonoglycerides. Acid anhydrides of alkyl fatty acids are commercially available or can be synthesized by conventional means.
The long chain fatty acids ~ se or naturally occurring fats and oils can serve as sources of the long chain saturated fatty acids. For example, soybean oil and high erucic acid rapeseed oil hydrogenated to an I.11. of about 10 or less are good sources of stearic and behenic fatty acids, respectively. Odd chain length long chain fatty acids can be derived from certain marine oils.
The esterification is conducted at temperatures of from about 20oC to reflux temperature of the solvent (about 50oC). Usually the esterification takes about 1 hour to about 5 hours.
The mole ratio of acid anhydride to 2-acylmonoglyceride is from about 1:1 to about 3:1 anhydride to monoglyceride. Too large an excess of anhydride may cause formation of triglycerides instead of the stereospecific 1,2-diacyl glycerides or 2,3-diacyl glycerides.
If necessary, the 1,2-diacyl glyceride or 2,3-diglyceride can be isolated by precipitation or crystallization.
The regiospecific 1,2-diacyl glycerides or 2,3 diacyl glycerides can be converted to stereospecific triglycerides by any conventional esterification reaction. Such techniques include esterification with acid chlorides or acid anhydrides under essentially anhydrous conditions (0.5% or less water). Other catalytic reactions which are known not to cause rearrange~~nt can be used. For example esterification with a fatty acid in the presence of 0.3% to about 1% (mole weight basis) of WO 91/16442 PCT/US91/02' 2~)~~~~~ - 12 -4,-N,N-dimethyl-aminopyridine can be used to make stereospecific triglycerides from 1,2-diacylglycerides. Catalysts which are known to induce rearrangement should be avoided as they will cause the 1,2-diacyl glyceride, 2,3-diacyl glyceride or the resultant triglyceride to rearrange, thus_producing a mixture of materials and not the regiospecific triglycerides that are desired.
The purified mixture of stereospecific triglycerides can also be subjected to bleaching and deodorizing steps for color and fla-vor/aroma improvement using conventional techniques well known in the fats and oils art. Alternatively, the reaction mixture can be bleached using conventional bleaching earth and/or activated carbon prior to purification. In the case of stereospecific triglycerides which have unsaturated fatty acid residues or mixtures of unsaturated and saturated fatty acid residues, the stereospecific triglycerides can be hydrogenated, before or after purification, to convert the unsaturated fatty acid residues to saturated fatty acid residues.
Uses of Stereospecific -Tri4lvcerides as Reduced Calorie Fats Stereospecific triglycerides of the type MML/MLM obtained according to the present invention (where L is a long chain saturated fatty acid residue and M is a medium chain saturated fatty acid residue) can be used as reduced calorie fats to partially or totally replace normal triglyceride fat in any fat-containing food composition comprising fat and nonfat ingredients to provide reduced calorie benefits. In order to obtain a significant reduction in calories, it is necessary that at least about 50% of the total fat in the food composition, or at least about 20% of the caloric value of the food, comprise the reduced calorie fat.
~0 Preparation of 2-Decanoyl glycerol.
Tridecanoin (45.0 mmole, 25.0 g) is dissolved in petroleum ether, b.p. 35oC -60oC, (600 ml) and n-butanol (110 ml). This solution ~~~9~'~~
is mixed with 0.05 M phosphate buffer (110 ml) containing LipolaseTM (Novo) 100L (9.0 g) and stirred at 37°C for 3 hours. After separation of phases, the organic solution is evaporated at reduced pressure and temperature (below 30°C) to a volume of about 100 ml.
This solution is diluted with hexane (500 ml) and cooled to -78°C using a dry ice-isopropanol bath. The precipitate is filtered below 0°C and dried. Yield of 2-decanolyl glycerol is 7.2 g (65%).
EXAMPLE II
Preparation of 2-octanoyl glycerol is obtained from trioctanolyl glycerol (53.2 mmole 25.0 g) in the presence of LipaseTM MAP from Amano (5.0 g) analogously to Example I with the yield 8.03 g (68%).
EXAMPLE III
Preparation of 1-Docosanolyl-1-decanolyl rac-glycerol A mixture of 2-decanoly glycerol from Example I (27.6 mmole, 6.8 g), docosanoic anhydride (30.2 mmole, 20.0 g) and immobilized IM-20 LipozymeTM from Novo (11.4 g) in methylene chloride (500 ml) is refluxed for 2 hours.
The lipozyme is from Novo. The enzyme is removed by filtration at room temperature. Upon cooling the filtrate to 0°C, docosanoic acid and anhydride precipitated and was filtered. The solution of product is further cooled to -78°C using a dry ice/isopropanol bath. The product is filtered and dried. The yield of 1-docosanolyl-2-decanoyl rac-glycerol is 12.9 g (81.6%).
_._...,.",r"
y' WO 91 / 16442 PCT/US91 /02' _ 14 _ EXANtPLE IV
1-Docosanoyl-2-octanoyl rac glycerol is obtained from 2-octanoyl glycerol (27.5 mmole, 6.0 g) and docosanoic anhydride (28.5 mmole, 18.9 g) in the presence of immobilized IM-20 Llpozyme (10.0 g) analogously to Example III. However, instead of cooling the final solution of product, methylene chloride is evaporated and the residue is dissolved in hexane. On cooling to -78oC the product precipitated. The yield after filtration was 9.s7 g (65%).
EXAMPLE V
1-Docosanoyl-2-decanoyl-3-octanoyl rac-glycerol.
A solution of 1-docosanoyl-2-decanoyl glycerol (24.6 mmole, 14.0 g), d~canoic anhydride (26.8 mmole, 7.25 g) and 4-N,N-dime'hylaminopyridine (DMAP) (1.25 mmole; 0.15 g) in methylene chloride (500 ml) is stirred at room temperature for 4 hours. Solvent is evaporated, the oily residuQ is dissolved in petroleum ether (500 ml) and cooled in dry ice. The precipitated product is filtered and dried under vacuum. Yi~ld of 1-docosanoyl-2-decanoyl-3-octanoyl rac-glycerol is 13.8 g (81%).
EXAMPLE VI
1-Docosane~:l-2-octanoyl-3-decanoyl rac-glycerol is prepared from 1-docosanoyl-2-octanoyl rac-glycerol (18.5 mmole. 10.0 g) and decanoic anhydride (18.5 mmole, 6.05 g) with DMAP (0.5 g) analogously to Example V with the yield 11 g (85'9).
EXAMPLE VII
2-Docosaneyi glycerol is obtained from 1,3-didecanoyl-2-docosanoyl glycerol (3.4 rnmole, 2.5 g) in the presence of lipase MAP (2.0 g) analogously to Example I. The time of hydrolysis in this case is 28 hours and the yield is 0.65 g (46%).
- '191 / 16442 PCT/US91 /02169 EXAMPLE VIII
1-Decanoyl-2-docosanoyl rac-glycerol is obtained from 2-docosanoyl glycerol (9.6 mmole, 4.0 g) and decanoic anhydride (9.6 mmole, 3.13 g) in the presence of immobilized Lipozyme (2.0 g) analogously to Example III with the yield 4.9 g (90%).
EXAMPLE IX
1-Decanoyl-2-docosanoyl-3-octanoyl rac-glycerol is prepared from 1-decanoyl-2-docosanoyl rac-glycerol (7.9 mmole, 4.5 g) and octanoic anhydride (7.9 mmole, 2.14 g) analogously to Example V
with the yield 4.1 g (75).
What is claimed is:
Also disclosed is a process for acylating a 2-acylglyceride by reacting an acid anhydride, immobilized lipase in a water immiscible solvent for from about 0.5 hours to about 5 hours at from about 20°C to about 50°C
temperature to form a stereoselective 1,2 diacylglyceride or 2,3-diglyceride.
Stereospecific 1,2,3-triacyl glycerols can be prepared by reacting the 1,2-diglycerides or 2,3-diglyceride with an acid anhydride or an acid chloride under anhydrous conditions in the presence of a chemical catalyst, e.g., 4-N,N-dimethylaminopyridine or an enzymic catalyst.
Other aspects of this invention are as follows:
A process for preparing 2-acylglycerides comprising:
(A) mixing the following ingredients for at least one hour at a temperature of from 20o C. to 50o C.
(1) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(2) from 20% to 60% of a water immiscible hydrocarbon;
(3) from 3% to 40% of a triglyceride:
~~i'~~~~
- 5a -(4) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglycerides;
(B) separating the water immiscible hydrocarbon containing -the 2-acylglyceride.
A process for preparing regiospecific 1,2-diacyl diglycerides or 2,3-diacyl diglycerides comprising the steps of:
(1) preparing a 2-monoacylglycerides by a process comprising:
(A) mixing the following ingredients for at least one hour at a temperature of from 20° C. to 50° C.:
(i) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(ii) from 20% to 60% of a water immiscible hydrocarbon (iii) from 3% to 40% of a triglyceride;
(iv) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglyceride;
(B) separating the immiscible hydrocarbon containing the 2-acylglyceride;
(2) reacting said 2-acylmonoglyceride with an acid anhydride, a catalytic amount immobilized lipase in a water immiscible hydrocarbon for from 0.5 hours to 5 hours at a temperature of from 20° C. to 50° C. to form a stereoselective 1,2-diacyl diglyceride or 2,3-diacyl diglyceride.
~.0~~8~8 - 5b -DETAILED DESCRIPTION OF THE INVENTION
Triglycerides prepared according to this invention generally have the formula:
C H O R' C HZ O R"
wherein R stands for an alkyl saturated or unsaturated fatty acid acyl group. R, R' and R" can be equal to each other.
The alkyl fatty acids used herein preferably have from about 2 to about 24 carbon atoms. Most preferably, the fatty acid in '~'O 91/16442 PCT/US91/02' '~
the 2 position has from 8 to 24 carbon atoms and fatty acids in the 1 and 3 positions, i.e. R and R", have from 8 to 24 carbon atoms. The fatty acids can be either saturated or unsaturated.
The unsaturated fatty acids can be mono unsaturated fatty acids or polyunsaturated fatty acids. The position occupied by R and R"
are the 1 and 3 positions, the position occupied by R' is the 2 position.
A. Definitions By "2-acylmonoglyceride" or "2-acylglyceride" is ~:eant a glycerol molecule esterified on the second carbon atoT: with a medium or long chain fatty acid.
By "medium chain fatty acid," as used herein, is :-.ant a saturated fatty acid, unsaturated fatty acid, or mixture thereof, having 6 to 10 carbon atoms.
By "medium chain fatty acid anhydride" as used herein, is meant the dehydration product of two medium chain fatty acids.
By "medium chain saturated fatty acid," as used herein, is meant C6 (caproic); Cg (caprylic), or C10 (capric) saturated fatty acids, or mixtures thereof. The C7 and Cg saturated fatty acids are not commonly found, but they are not excluded frog the possible medium chain fatty acids. The present media;- chain fatty acids do not include lauric acid (C12), sometimes referred to in the art as a medium chain fatty acid.
By "long chain fatty acid," as used herein, is meant a satu-rated fatty acid, unsaturated fatty acid, or mixture t!~~reof, havino 14 to 24 carbon atoms.
By "long chain saturated fatty acid," as used her~~n, is meant Clg (stearic), C1g {nonadecylic), C20 (arachidic'" C21 (heneicosanoic), C22 (behenic), C23 (tricosanoic), or C24 (lignoceric) saturated fatty acids, or mixtures there;.
As used herein, the term "comprising" means various components or steps can be conjointly employed in the :resent invention. Accordingly, the term "comprising" encompa:~es the more restrictive terms "consisting essentially of" and 'consisting of."
-"'~ 91 / 16442 ~ ~ ~ ~1 ~ ~ ~ PCT/US91 /02169 -All percentages, ratios and proportions used herein are by weight unless otherwise specified.
Hydrolysis of triglycerides to 2-monoacylglyceride is carried out in a two phase mixture of hydrocarbon and the starting triglycerides in a water immiscible phase and an aqueous phase comprising the buffer and a 1,3-specific lipase. The lower alkyl alcohol partitions between the aqueous phase and the organic phase.
The presence of alcohol has two functions. It inhibits hydrolysis of 2-acylglycerides to glycerol and it drives the reaction towards 2-monoglyceride. In its absence, the process reaches early steady state characterized by high concentrations of triglycerides and diglycerides. Thus, extension of the reaction time in the absence of alcohols would not result in better yielas of di- or monoglycerides but in the formation of glycerol. The higher straight chain alkyl alcohols, those having six or more carbon atoms, are less efficient or do not work. The alcohols that can be used herein are methanol, the primary butyl alcohols and the primary pentyl alcohols and 2-butanol. The preferred alcohols are 1-butanol, isobutanol and secondary butanol. The propyl alcohols do not work in this reaction nor does ethanol.
The primary butanols are 1-butanol and 2-methyl-1-propanol.
The primary pentanols are 1-pentanol, 2-methyl-1-butanol, and 3-methyl-1-butanol. The only secondary alcohol that functions :o produce the high yields of 2-acyl glycerides in the process of this invention is 2-butanol.
Any 1,3-specific lipase can be used for the hydrolysis. Tha ''0 lipases derived from the species asper9illus and rhizopus can be used. Specific lipases include aspergillus oryzae, aspergillus niger, mucor javanicus, mucor miehei, pancreatic, rhizopus delamar, rhizopus japonicus. These include MAP from Amano {Japan), lipolase and lipozyme from Novo (Netherlands). The amount of enzyme used is the amount of enzyme necessary to WO 91/16442 PCT/US91/0?.~~ '~
_ g _ catalyze the reaction at a reasonable rate. Too slow a rate will cause the concentration of diglycerides to increase.
The enzyme concentration depends upon the amount of active protein in the enzyme preparation. Enzyme can be dried, immobilized on a resin or covalently bonded to or abbsorbed on a support, or be in solution. The concentration needed to hydrolyze the triglyceride depends upon the form, the type and the activity of the enzyme. The amount required~is a catalytic amount. A
catalytic amount is enough to have the enzyme produce required 2-acyl glyceride at a reasonable rate but not so much as to force the reaction to form glycerine. One skilled in the art can easily determine the catalytic amount by running a small scale reaction and looking at the final products.
The triglyceride which has tt~,e requisite alkyl fatty acid in the 2 position is dissolved in a hydrocarbon. The preferred hydrocarbons are the hexanes, petroleum ether, or isooctane. Any water immiscible hydrocarbon solvent which is essentially inert to the lipase can be used. Some solvents can denature enzymes. The solvent must dissolve the triglyceride at the temperature of the reaction. Since these triglycerides can be used in foods and pharmaceuticals, a food approved or edible hydrocarbon should be used. The hydrocarbon can be an alkane with from 5 to 10 carbons, an aromatic hydrocarbon such as benzene, toluene or xylene or halogenated hydrocarbons such as chloroform, methylene chloride or carbon tetrachloride. The preferred hydrocarbon solvents are hexane, pentane, petroleum ether and isooctane.
From about 3% to about 60% triglyceride is used in the reaction. Triglycerides which can be utilized in the hydrolysis reaction include triglycerides ha~~ing C4 to C26 hydrocarbon chains with three fatty acid moieties. Ti'tese materials can be derived from plants or animals or can be edible synthetic fats or oils.
Liquid oils, e.g., unsaturated vegetable oils, can be used. Solid fats work only to the extent they are soluble in the solvent.
These oils can be partially hydrogenated to convert some of the unsaturated double bonds of the fatty acid constituents into "'~ 91/16442 ~ ~ ~ ~ ~~ ~ PCT/US91/02169 _g_ saturated bonds. Vegetable oils include soybean oil, hazelnut oil, linseed oil, olive oil, peanut oil, canola oil, safflower oil, rapeseed oil, cottonseed oil and sunflower seed oil can also be used herein.
Also suitable for use herein are the so-called low molecular weight synthetic fats which are certain tri- or diglycerides in which one or two of the hydroxyl groups of the glycerine have been esterified with acetic, propionic, butyric, hexanoic, capric or caprylic acids and one or two of the remaining hydroxyl groups of the glycerine have been esterified with a mixture of higher molecular weight fatty acids having from 8 to 22 carbon atoms.
Especially preferred for use herein are syr,Jretrical trigiycerides as, e.g., tridecanoin or trioctanoin.
Other common types of triglycerides include: cocoa butter and cocoa butter substitutes, such as shea and illipe butter; milk fats, such as butter fat; and marine oils which can be converted into plastic or solid fats such as menhaden, pilcherd, sardine, whale and herring oils.
Preferred triglycerides are those derived from vegetable oils. These can be hydrogenated and unhydrogenated oils.
Triglycerides of octanoic acid, decanoic acid and dodecanoic acid are preferred for use herein. Any unsaturated triglyceride containing unsaturated fatty acids is also preferred, e.g.
triolein. The triglycerides of long chain fatty acids are usually not soluble in the hydrocarbon solvent or are solid at the reaction temperature. Therefore they are not preferred for use herein.
The aqueous solution of the enzyme is buffered to a pH of about 4 to about 8. Standard buffer solutions which are not ~'0 incompatible with the enzyme can be used. These include the phosphate buffers.
The reaction mixture has the following proportions by weight percent:
3% to 40% triglyceride 15% to 25% aqueous buffer WO 91/16442 PCT/US91/02' ~~
2()'~9~~~ - to -lOX to 25% alcohol 20X to 60% hydrocarbon The preferred ratio of alcohol to triglyceride is based on the amount of fatty acid generated by the hydrolysis. The alcohol serves several functions in this reaction. It reacts with the fatty acid to make an alkyl ester driving the reaction toward the 2-acyl glyceride; and it modifies any association structures present in the reaction mixture. When the alcohol is insoluble in water, it can be substituted for the hydrocarbon if the triglyceride is soluble in the alcohol.
The reaction is carried out at ambient tempera~ure or at temperatures of from about 20oC to about 50oC for fr~~~~ 0.5 hours to about 8 hours. The reaction is mixed using a standard laboratory mixer.
The hydrocarbon layer is separated from the aquaous phase.
The 2-acylglyceride is present in the hydrocarbon phase. Any conventional separation technique can be used.
For example, the 2-acylglyceride can be isolated from the organic phase by crystallization or evaporation of the organic solvent. Liquid 2-acylmonoglycerides can be purified by distillation however, distillation frequently causes rearrangement or isomerization to 1-acyl-glycerides.
The 2-acylmonoglycerides can be esterified stereoselectively using acid anhydrides. It is not necessary to isolate the 2-monoacylglycerides from the organic phase if they are to be esterified. F!owever, the solution should be dried to less than about 0.5% water to prevent hydrolysis of the acid ~rhydride. Any suitable drying agent such as magnesium sulfate, calcium chloride or other inert drying aid can be used. Excess anhy3ride could also be used, but this is less economical.
The excess lower alkyl alcohol should also be removed since it too can react with the acid anhydride to form the corresponding ester.
The 2-monoacylglyceride is reacted with an acid anhydride in an organic solvent. Any hydrocarbon, either alkyl or aromatic, or halogenated hydrocarbon can be used for this reaction. For '- ~ 91/16442 ~ ~ ~ ~ ~ ~ PCT/US91/02169 example, petroleum ether, hexane, benzene, toluene, chloroform, methylene chloride and octane can be used.
A 1,3-specific lipase is added to the hydrocarbon mixture.
The same lipases as were used to prepare the 2-acylmonoglycerides are suitable for this reaction. They include immobilized lipases and liposomes which are preferred. Catalytic amounts of lipase are used.
Any acid anhydride can be used to esterify the 2-acylmonoglycerides. Acid anhydrides of alkyl fatty acids are commercially available or can be synthesized by conventional means.
The long chain fatty acids ~ se or naturally occurring fats and oils can serve as sources of the long chain saturated fatty acids. For example, soybean oil and high erucic acid rapeseed oil hydrogenated to an I.11. of about 10 or less are good sources of stearic and behenic fatty acids, respectively. Odd chain length long chain fatty acids can be derived from certain marine oils.
The esterification is conducted at temperatures of from about 20oC to reflux temperature of the solvent (about 50oC). Usually the esterification takes about 1 hour to about 5 hours.
The mole ratio of acid anhydride to 2-acylmonoglyceride is from about 1:1 to about 3:1 anhydride to monoglyceride. Too large an excess of anhydride may cause formation of triglycerides instead of the stereospecific 1,2-diacyl glycerides or 2,3-diacyl glycerides.
If necessary, the 1,2-diacyl glyceride or 2,3-diglyceride can be isolated by precipitation or crystallization.
The regiospecific 1,2-diacyl glycerides or 2,3 diacyl glycerides can be converted to stereospecific triglycerides by any conventional esterification reaction. Such techniques include esterification with acid chlorides or acid anhydrides under essentially anhydrous conditions (0.5% or less water). Other catalytic reactions which are known not to cause rearrange~~nt can be used. For example esterification with a fatty acid in the presence of 0.3% to about 1% (mole weight basis) of WO 91/16442 PCT/US91/02' 2~)~~~~~ - 12 -4,-N,N-dimethyl-aminopyridine can be used to make stereospecific triglycerides from 1,2-diacylglycerides. Catalysts which are known to induce rearrangement should be avoided as they will cause the 1,2-diacyl glyceride, 2,3-diacyl glyceride or the resultant triglyceride to rearrange, thus_producing a mixture of materials and not the regiospecific triglycerides that are desired.
The purified mixture of stereospecific triglycerides can also be subjected to bleaching and deodorizing steps for color and fla-vor/aroma improvement using conventional techniques well known in the fats and oils art. Alternatively, the reaction mixture can be bleached using conventional bleaching earth and/or activated carbon prior to purification. In the case of stereospecific triglycerides which have unsaturated fatty acid residues or mixtures of unsaturated and saturated fatty acid residues, the stereospecific triglycerides can be hydrogenated, before or after purification, to convert the unsaturated fatty acid residues to saturated fatty acid residues.
Uses of Stereospecific -Tri4lvcerides as Reduced Calorie Fats Stereospecific triglycerides of the type MML/MLM obtained according to the present invention (where L is a long chain saturated fatty acid residue and M is a medium chain saturated fatty acid residue) can be used as reduced calorie fats to partially or totally replace normal triglyceride fat in any fat-containing food composition comprising fat and nonfat ingredients to provide reduced calorie benefits. In order to obtain a significant reduction in calories, it is necessary that at least about 50% of the total fat in the food composition, or at least about 20% of the caloric value of the food, comprise the reduced calorie fat.
~0 Preparation of 2-Decanoyl glycerol.
Tridecanoin (45.0 mmole, 25.0 g) is dissolved in petroleum ether, b.p. 35oC -60oC, (600 ml) and n-butanol (110 ml). This solution ~~~9~'~~
is mixed with 0.05 M phosphate buffer (110 ml) containing LipolaseTM (Novo) 100L (9.0 g) and stirred at 37°C for 3 hours. After separation of phases, the organic solution is evaporated at reduced pressure and temperature (below 30°C) to a volume of about 100 ml.
This solution is diluted with hexane (500 ml) and cooled to -78°C using a dry ice-isopropanol bath. The precipitate is filtered below 0°C and dried. Yield of 2-decanolyl glycerol is 7.2 g (65%).
EXAMPLE II
Preparation of 2-octanoyl glycerol is obtained from trioctanolyl glycerol (53.2 mmole 25.0 g) in the presence of LipaseTM MAP from Amano (5.0 g) analogously to Example I with the yield 8.03 g (68%).
EXAMPLE III
Preparation of 1-Docosanolyl-1-decanolyl rac-glycerol A mixture of 2-decanoly glycerol from Example I (27.6 mmole, 6.8 g), docosanoic anhydride (30.2 mmole, 20.0 g) and immobilized IM-20 LipozymeTM from Novo (11.4 g) in methylene chloride (500 ml) is refluxed for 2 hours.
The lipozyme is from Novo. The enzyme is removed by filtration at room temperature. Upon cooling the filtrate to 0°C, docosanoic acid and anhydride precipitated and was filtered. The solution of product is further cooled to -78°C using a dry ice/isopropanol bath. The product is filtered and dried. The yield of 1-docosanolyl-2-decanoyl rac-glycerol is 12.9 g (81.6%).
_._...,.",r"
y' WO 91 / 16442 PCT/US91 /02' _ 14 _ EXANtPLE IV
1-Docosanoyl-2-octanoyl rac glycerol is obtained from 2-octanoyl glycerol (27.5 mmole, 6.0 g) and docosanoic anhydride (28.5 mmole, 18.9 g) in the presence of immobilized IM-20 Llpozyme (10.0 g) analogously to Example III. However, instead of cooling the final solution of product, methylene chloride is evaporated and the residue is dissolved in hexane. On cooling to -78oC the product precipitated. The yield after filtration was 9.s7 g (65%).
EXAMPLE V
1-Docosanoyl-2-decanoyl-3-octanoyl rac-glycerol.
A solution of 1-docosanoyl-2-decanoyl glycerol (24.6 mmole, 14.0 g), d~canoic anhydride (26.8 mmole, 7.25 g) and 4-N,N-dime'hylaminopyridine (DMAP) (1.25 mmole; 0.15 g) in methylene chloride (500 ml) is stirred at room temperature for 4 hours. Solvent is evaporated, the oily residuQ is dissolved in petroleum ether (500 ml) and cooled in dry ice. The precipitated product is filtered and dried under vacuum. Yi~ld of 1-docosanoyl-2-decanoyl-3-octanoyl rac-glycerol is 13.8 g (81%).
EXAMPLE VI
1-Docosane~:l-2-octanoyl-3-decanoyl rac-glycerol is prepared from 1-docosanoyl-2-octanoyl rac-glycerol (18.5 mmole. 10.0 g) and decanoic anhydride (18.5 mmole, 6.05 g) with DMAP (0.5 g) analogously to Example V with the yield 11 g (85'9).
EXAMPLE VII
2-Docosaneyi glycerol is obtained from 1,3-didecanoyl-2-docosanoyl glycerol (3.4 rnmole, 2.5 g) in the presence of lipase MAP (2.0 g) analogously to Example I. The time of hydrolysis in this case is 28 hours and the yield is 0.65 g (46%).
- '191 / 16442 PCT/US91 /02169 EXAMPLE VIII
1-Decanoyl-2-docosanoyl rac-glycerol is obtained from 2-docosanoyl glycerol (9.6 mmole, 4.0 g) and decanoic anhydride (9.6 mmole, 3.13 g) in the presence of immobilized Lipozyme (2.0 g) analogously to Example III with the yield 4.9 g (90%).
EXAMPLE IX
1-Decanoyl-2-docosanoyl-3-octanoyl rac-glycerol is prepared from 1-decanoyl-2-docosanoyl rac-glycerol (7.9 mmole, 4.5 g) and octanoic anhydride (7.9 mmole, 2.14 g) analogously to Example V
with the yield 4.1 g (75).
What is claimed is:
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing 2-acylglycerides comprising:
(A) mixing the following ingredients for at least one hour at a temperature of from 20° C. to 50° C.
(1) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(2) from 20% to 60% of a water immiscible hydrocarbon;
(3) from 3% to 40% of a triglyceride;
(4) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglycerides;
(B) separating the water immiscible hydrocarbon containing the 2-acylglyceride.
(A) mixing the following ingredients for at least one hour at a temperature of from 20° C. to 50° C.
(1) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(2) from 20% to 60% of a water immiscible hydrocarbon;
(3) from 3% to 40% of a triglyceride;
(4) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglycerides;
(B) separating the water immiscible hydrocarbon containing the 2-acylglyceride.
2. A process for preparing regiospecific 1,2-diacyl diglycerides or 2,3-diacyl diglycerides comprising the steps of:
(1) preparing a 2-monoacylglycerides by a process comprising:
(A) mixing the following ingredients for at least one hour at a temperature of from 20° C. to 50° C.;
(i) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(ii) from 20% to 60% of a water immiscible hydrocarbon;
(iii) from 3% to 40% of a triglyceride;
(iv) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglyceride;
(B) separating the immiscible hydrocarbon containing the 2-acylglyceride;
(2) reacting said 2-acylmonoglyceride with an acid anhydride, a catalytic amount immobilized lipase in a water immiscible hydrocarbon for from 0.5 hours to 5 hours at a temperature of from 20° C. to 50° C. to form a stereoselective 1,2-diacyl diglyceride or 2,3-diacyl diglyceride.
(1) preparing a 2-monoacylglycerides by a process comprising:
(A) mixing the following ingredients for at least one hour at a temperature of from 20° C. to 50° C.;
(i) from 15% to 25% of an aqueous buffer having a pH of from 4 to 8 containing a catalytic amount of 1,3-specific lipase enzyme;
(ii) from 20% to 60% of a water immiscible hydrocarbon;
(iii) from 3% to 40% of a triglyceride;
(iv) from 10% to 25% of a lower alkyl alcohol selected from the group consisting of methanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-propanol, and primary alkyl alcohols having 5 carbon atoms to form 2-acylglyceride;
(B) separating the immiscible hydrocarbon containing the 2-acylglyceride;
(2) reacting said 2-acylmonoglyceride with an acid anhydride, a catalytic amount immobilized lipase in a water immiscible hydrocarbon for from 0.5 hours to 5 hours at a temperature of from 20° C. to 50° C. to form a stereoselective 1,2-diacyl diglyceride or 2,3-diacyl diglyceride.
3. A process according to claim 1 wherein said enzyme is immobilized on a support.
4. A process according to claim 3 wherein said hydrocarbon is selected from the group of consisting of alkyl hydrocarbons having from 5 to 10 carbons.
5. A process according to claim 4 wherein said triglyceride is selected from the group consisting of fatty acid triglycerides wherein said fatty acids have from 8 to 24 carbon atoms.
6. A process according to claim 5 wherein said triglyceride is selected from the group consisting of partially hydrogenated and unhydrogenated sunflower seed oil, soybean oil, canola, rapeseed oil, safflower oil, marine oils, corn oil and mixtures thereof.
7. A process according to claim 5 wherein said triglyceride contains octanoic acid or decanoic acid in the 2-position.
8. A process according to claim 2 wherein said alcohol is selected from the group consisting of methanol, 1-butanol, 1-pentanol and 2-methyl-1-propanol.
9. A process according to claim 8 wherein said enzyme is immobilized on a support.
10. A process according to claim 9 wherein said hydrocarbon is selected from the group of consisting of hexane, pentane, isooctane, petroleum ether and mixtures thereof.
11. A process according to claim 10 wherein said triglyceride is selected from the group consisting of fatty acid triglycerides wherein said fatty acids have from 8 to 24 carbon atoms.
12. A process according to claim 11 wherein said triglyceride is selected from the group consisting of partially hydrogenated and unhydrogenated sunflower seed oil, soybean oil, canola, rapeseed oil, safflower oil, marine oils, corn oil and mixtures thereof.
13. A process according to claim 12 wherein said triglyceride contains octanoic acid or decanoic acid in the 2-position.
14. A process according to claim 13 wherein said water-immiscible hydrocarbon in step 2 is selected from the group consisting of benzene, toluene, hexane, petroleum ether, methylene chloride, chloroform and mixtures thereof.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/511,115 US5116745A (en) | 1990-04-19 | 1990-04-19 | Process for preparing 2-acylglycerides or 1,2-diacyl diglycerides or 2,3-diacyl diglycerides |
US511,115 | 1990-04-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2079888A1 CA2079888A1 (en) | 1991-10-20 |
CA2079888C true CA2079888C (en) | 1998-10-06 |
Family
ID=24033508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002079888A Expired - Lifetime CA2079888C (en) | 1990-04-19 | 1991-04-01 | Process for preparing 2-acylglycerides or 1,2-diacyl diglycerides or 2,3diacyl diglycerides |
Country Status (4)
Country | Link |
---|---|
US (1) | US5116745A (en) |
EP (1) | EP0528813A4 (en) |
CA (1) | CA2079888C (en) |
WO (1) | WO1991016442A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5137660A (en) * | 1991-03-15 | 1992-08-11 | The Procter & Gamble Company | Regioselective synthesis of 1,3-disubstituted glycerides |
IN185750B (en) * | 1997-12-08 | 2001-04-21 | Council Scient Ind Res | |
US6835408B2 (en) * | 1998-11-13 | 2004-12-28 | The Nisshin Oillio Group, Ltd. | Oil or fat composition |
US20030054509A1 (en) * | 2001-04-06 | 2003-03-20 | Archer-Daniels-Midland Company | Method for producing fats or oils |
US7452702B2 (en) | 2003-07-16 | 2008-11-18 | Archer-Daniels-Midland Company | Method for producing fats or oils |
DE102004019472A1 (en) * | 2004-04-22 | 2005-11-17 | Bayer Healthcare Ag | phenylacetamides |
DE102005002711A1 (en) * | 2005-01-19 | 2006-07-27 | Cognis Deutschland Gmbh & Co. Kg | Production and use of monoglycerides |
DE102005002700A1 (en) * | 2005-01-19 | 2006-07-27 | Cognis Deutschland Gmbh & Co. Kg | Compositions usable as biofuel |
UA97127C2 (en) * | 2006-12-06 | 2012-01-10 | Бандж Ойлз, Инк. | Method and system for the enzymatic treatment of lipid containing feedstock |
AU2009295982A1 (en) | 2008-09-23 | 2010-04-01 | Basf Plant Science Gmbh | Plants with increased yield (LT) |
EP2809789B1 (en) | 2012-01-30 | 2018-09-12 | Arvind Mallinath Lali | Enzymatic process for fat hydrolysis in a polar organic solvent |
WO2017003992A1 (en) | 2015-07-02 | 2017-01-05 | Stepan Company | Method for preparing 2-monoacylglycerides |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0064855B1 (en) * | 1981-05-07 | 1986-09-17 | Unilever Plc | Fat processing |
EP0126416B1 (en) * | 1983-05-19 | 1988-01-07 | Asahi Denka Kogyo Kabushiki Kaisha | Reaction method for transesterifying fats and oils |
JPS60234590A (en) * | 1984-05-07 | 1985-11-21 | Asahi Denka Kogyo Kk | Hydrolysis of oil or fat |
SE452166B (en) * | 1986-03-10 | 1987-11-16 | Berol Kemi Ab | PROCEDURE FOR TRANSESTERIFICATION OF TRIGLYCERIDES |
US4865978A (en) * | 1986-07-03 | 1989-09-12 | The United States Of America As Represented By The Secretary Of Agriculture | Lipolytic splitting of fats and oils |
JPS6419042A (en) * | 1987-07-14 | 1989-01-23 | Nisshin Oil Mills Ltd | Production of fat and oil |
JP2571587B2 (en) * | 1987-12-22 | 1997-01-16 | 旭電化工業株式会社 | Method of transesterifying fats and oils |
WO1990004033A1 (en) * | 1988-10-04 | 1990-04-19 | Enzytech, Inc. | Production of monoglycerides by enzymatic transesterification |
US5149642A (en) * | 1990-04-20 | 1992-09-22 | The Procter & Gamble Company | Process for preparing 2-acylglycerides or 1,2 or 2,3-diacylglycerides |
-
1990
- 1990-04-19 US US07/511,115 patent/US5116745A/en not_active Expired - Lifetime
-
1991
- 1991-04-01 WO PCT/US1991/002169 patent/WO1991016442A1/en not_active Application Discontinuation
- 1991-04-01 CA CA002079888A patent/CA2079888C/en not_active Expired - Lifetime
- 1991-04-01 EP EP19910907129 patent/EP0528813A4/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
EP0528813A1 (en) | 1993-03-03 |
EP0528813A4 (en) | 1993-07-21 |
WO1991016442A1 (en) | 1991-10-31 |
US5116745A (en) | 1992-05-26 |
CA2079888A1 (en) | 1991-10-20 |
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